Metal compounds of orthooxyazo dyestuffs and a process of making same.



UNITED STATES PAT] ENT OFFICE.

CARL JAGERSPACHER, OF BASEE, SWITZERLAND, ASSIGNOR TO SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF BASEL, SV'ITZERLAND.

METALCOMPOUNDS OF ORTHOOXYAZO DYESTUFFS ANJ) A PROCESS OF MAKING SAME.

.Be it known that I, Dr. CARL .Iaonns- PAcmsR, chemist, a citizen of the SWISS Rea public, and resident of Basel, Switzerland,

have invented new and useful Metal Compounds of Orthooxyazo Dyestuffs and a Process of Making Same, of which the following is a full, clear, and exact specification.

In my application for U. S. Letters Patent Serial No. 69652, filed December 31, 1915, is :described a process for the manufacture of new orange to red-orthooxyazo dyestufi's able to be combined with chromium, consisting in combining the diazo derivatives of orthoaminophenols or of orthoaminonaphthols or of their derivates with the py'razolone derivates of the benzene or the naphthalene series substituted by hydroxyl in the aryl-nucleus.

I have now found that these dyestuffs can be transformed into new metal compounds, soluble in water, by their treatment with convenient metal compounds, the said new metal compounds having the valuable property to dye the animal fibers in an acid bath vivid tints showing an excellent fastness to washing and to light without any subsequent treatment. Thus the transformation of the said dyestuffs into copper compounds soluble in water is effected for instance, by treating the same with copper compounds in an aqueous solution or suspension accord ing to the process described in the United States applications .for Letters Patent Scr. No. 43413, filed August 3, 1.915, and Scr. No. 54503 and No. 54504, both filed October '7, 1915. Generally speaking, the new copper compounds from which the copper cannot any more be precipitated by sodium carbonate, soda lye and ammonia, separate directly from the reaction mass. If that should not be the case, their separation can be produced by addition of common salt.

Instead of starting from the achieved orthooxyazo dyestuffs and acting on their solution or suspension with copper com- )ounds, the new copper compounds can be ibtained by producing the said orthooxyazo lyestufi's in presence of copper compounds. Iereby are produced directly the heretofore pecified copper compounds, which are, evenial 1y after addition of common salt, filtered, washed and dried. The copper compounds reduced according to the described process Specification of Letters Patem.

Application filed December 31, 1915.

Patented Feb. 20, 1917.

Serie 1 No. 69,651.

yield from acid baths on animal fibers valuable orange to brown and red dyein s a showing a "cry good fastness to light, was 1- the new metal compounds contain, besidesv the hydrox] '1 group resulting from the orthooxydiazo cnnpound, till a further group able to. be combined with chromium, they allow to p1 oduce tints also fast to fulling and potting, by treating subsequently their direct dyeings with chromates or by dyeing the said metal compounds according to other processes usually employed for mor; dant dyestuffs.

The prepiration of the new copper compounds is illustrated by the following examples:

Example 1: 23 parts of the dyestufl derived from the diazo compound of 4:2:1- uitroamiuo henol and the pyrazolone corresponding to the orthoaminophenol-sulfonic acid, are dissolved in 800 parts hot water and lo the thus obtained solution is added at ab )ut 70 C. a solution of 13,parts copper sulfate in 50 parts water. The red solution tur is to brown and the red-brown copper compound precipitates entirely after common salt has been added. The sulfuric acid which became free is neutralized with sodium arel ate. the copper compound is separated b, filtration, pressed and dried. The dyestull' yields from an acid bath on animal fiber; orange-brown dyeings fast to washing and light.

Example 5%: To an aqueous solution of 27 parts of the methylpyrazolone derived from orthoamino henolsulfonic acid and of 40 parts sodiun carbonate is added a solution of 25 'gparts cry stallized copper sulfate in 100 parts water. I ate the thus obtained mixture is introduced hereafter the diazo derivative prepared in the known manner from 18.9 parts of orthoaminophenolsulfonic acid. After the c(mbination' has taken place'the copper hydr oxid in excess is separated by filtering the mass hot and from the filtered liquid the cc pper compound of the dyestufi' is precipitated by adding common salt. It dyes wooLin an acid bath brown-orange tints fast to light, w ashing and alkali.

In an analogous manner is effected the preparation of the copper compounds of the various other dyestuffs described in my application for U. S. Letters Patent Serial No. 69652, filed December 31, 1915.

Instead of roducing the new copper compounds in su stance, they can be prepared on the fiber, by treating the dyeings di rectly obtained with the dyestufi'sof my application for U. S. Letters Patent Serial No. 69652. filed December 31, 1915, subsequently with copper salts or by dyeing with the said dyestuffs in a bath containing copper salts.

The transformation of the dyestuffs described in my application for U. S. Letters Patent executed at the same date as the present one into well defined chromium compounds is effected for instance by treating the said dyestufl's with chromium oxid salts in an-hot aqueous solution or suspension till the itransformation is complete and by separating the thus formed chromium compounds by salting out orby evaporation.

Instead of starting from the said dyestufl 's for the preparation of the new chromium compounds, these latter can be produced also by subjecting the half chromed dyestuffs able to be prepared according to the application for U. S. Letters Patent Serial No. 64023, filed November 29,1915, by combining the chromium derivates of orthooxydiazo compounds with oxyphenylor oxynaphthylpyra-zolones, to a further action of chromium ozud salts.

' The preparation of the chromium comppunds is illustrated by the. following examp e:

Example 3: 5 parts of the dyestuif prepared according to Example 1 of my application for U. S. Letters Patent executed at the same date as the present one with the diazo derivate of orthoaminophenolsulfonic acid and the pyrazolone derived from paranitroorthoaminophenol are dissolved in 100 parts water and to the thus obtained solution are added 12 parts crystallized sodium acetate and 5 parts chromium fiuorid and the mass boiled feebly for about if to 1 hour, whereby the coloration of the solution passes from yellow to orange. Hereafter the liquid is separated by filtration from small quantities of inorganic components, evaporated to the half of its volume and the new chromium compound is separated in a solid form by adding common salt to the cooled solution. It dissolves in water with redorange coloration and from its aqueous solution it dyes animal fibers fast red-orange tints identical with those-obtained by chromating subsequently the dyeings of the sodium salt of the dyestuif.

In an analogous manner can be prepared the chromium compounds of the various dyestuffs described inniy application for U. S. Letters Patent Serial No. 69652, filed December 31. 1915.

In the following tabular exhibit are indicated the properties of a certain number of the metal compounds able to be prepared according to the present invention:

Dycstuil resulting irom i Dyeing f n the chr0- i 25 21 miumlcom- The methyl pyramind on WOOl R zolone derived g i dmm an acid hath. 001 [rpm .c an acid bath.

Para-nitro-orthd o-Amin op henol- Orange-brown. R e (l o raminophenol. suli'onic acid. angc.

Ortho-aminophe o-A min 0 p h enol- Orange-brown. R e d o r nolsulionic acid. sulionic acid. ange.

Orthoamincphe- Para-nitro-ortho- Orange-brown. R e d o r nolsulionic acid. aminophenol. a ge.

Ortho-aminophe- Nitroamino-para- R d: Red.

nolsulionic acid. cresol.

Ortho-aminophe- Picramicacid Brown Brown.

nolsulionic acid. I

Ortho-aminophe- 1:2:4-Amino-nap Red Blue-red.

nolsulionic acid. tholsulionic acid.

Parachlor-orthoo-A min ophenol Orange-brown e d 0r aminophenol. sulionic acid. I ange.

Para-ehlor-orth0- Ortho-amino-para Brown-red Red.

aminophenol. cresol-sulfonic acid.

Para-amino salilyc o-Amin op henol- Orange R e d o racid. sullonic acid. ange.

Pata-aminosalily p -N' ro-o-amino- Brown-orange. R e d o 1- acid. phenol. ange.

Para-aminosahlyc o-Aminool- Red-orange; Red.

acid. sulionic acid.

Para-aminosalilyc Nitroaniino-p-cre- Red Red.

acid. sol.

Pam-amincsalilyc p Chlor-o-amin0 Red-orange... Red.

acid. phenol.

Para-aminosalil yc p-Chlor-o-amiiio- Rod-orange. Red.

acid. phenol-o-suli'onic acid.

Para-eminosslilyc Picmmic acid. Brow-n R e d acid. brown.

Para-aminosalilyc 3 ;2:4-Amino-naph- Blue-red Red. acid. tholsulfomc acid.

2 5 7- Aminoo-Aminophe n o l Brown Brown.

naphtholsulsullonic acid. ionic acid.

2 z 5 7-Amlnop-Nitro-o-amln 0- Brown Brown.

naphtholsulphenol. ionic acid. I

2 z 5 7 -Amino- 1 :2:4-Aminonaph- Red Blue-red.

naphtho 1 5|! l tholsullunic acid. ionic acid.

4-Sulio-2 amino-lp-Nitro-o-ami n o Orange-brown. Red-brown.

phenol 6 carpheno oxylic acid.

-4-Sulio-2-amino-1- N itroamJno-p-cre- Yellow-red Pure vel phenol fi-carsol. low-re oxylic acid.

oxyazo dyestuffs, consisting in treating with metal com ounds the orthooxyazo dyestuffs resulting rom the combination of orthooxylfliazo bodies with pyrazolone-derivates of the benzene or the naphthalene series hydroxylated in the aryl nucleus, in order to transform the said orthooxyazo dyestufi's into products containing a metal and soluble in water.

2. The described process for the manufacture of new copper compounds of orthooxyazo' dyestulfs consisting in treating with copper compounds the orthooxyazo dyestuffs resulting from the combination of orthooxydiazo bodies with pyrazolone derivates of the benzene or the naphthalene series hydroxylated in the aryl nucleus, in order to convert the said orthooxyazo dyestuffs into products containing copper and soluble in water.

3. The described process for the manufacture of new copper compounds of orthooxyazo dyestufls consisting in combining orthooxydiazo bodies with pyrazolone derivates= of the benzene c r the naphthalene series hydroxylated in th e aryl nucleus in presence of copper compoulds, in order to obtain compounds of orthc oxyazo dyestuffs containing copper and soluble in water.

4. As new products, the described metal compounds of )rthooxyazo dyestuffs, constituting in a dry state yellow to red powders dissolving in concentrated sulfuric acid to deep colored solutions and in water to yellow to led colored solutions from which animal fibers are dyed yellow to brown and orange to red tints fast to light, washing and a1.- ra-li and becoming also fast to fulling and potting by chromating them subsequently. 5. As new articles of manufacture, the described new copper compounds of orthooxyazo dyestufii, constituting in dry state yellow to red powders, dissolving in concentrated sulfuric acid to deep colored solutionsand 1n wal er to yellow to red solutions dyeing animal fibers yellow, brown and orange'to red til ts fast to light, washing and alkali and becoming potting by chro1 natmg them subsequently.

In witness wh areof I have hereunto signed my name this second day of December 1915, in the presence of two subscribin witnesses.

DR. CARL JAGERSP CHER.

Witnesses:

ARNOLD 2 mum, AMAND H mm.

also fast to fulling and I 

